Calcium Bismuthate Nanoparticulates with Orthorhombic and Rhombohedral Crystalline Lattices: Effects of Composition and Structure on Photoactivity. Issue 30 (25th October 2017) - Shtarev, Dmitry S.
Abstract: Calcium bismuthate nanoparticles with orthorhombic and rhombohedral crystal lattices were synthesized and characterized by various techniques. The syntheses caused the formation of oxygen and cationic vacancies in bismuth‐deficient samples. Heat treatment of samples with anionic vacancies led to thermal annealing of oxygen vacancies in ambient air; the annealing process was reversible. Oxygen vacancies in Bi‐deficient CaBi6 O10 governed the optical absorption beyond the fundamental absorption edge at E(hν) < Ebg ≈ 2.5 eV. Bandgap energies of the bismuthates with orthorhombic and rhombohedral lattices were 2.51 eV prior to annealing and 2.47 eV after annealing at 350 °C. The trend in photoactivity toward the degradation of methylene blue dye under visible light showed that the photoactivity of the orthorhombic samples ( 1‐3 ) increased with a decrease in the [Ca]:[Bi] ratio (1.0:6.3 to 1.0:4.3); the sample with lowest ratio (1.0:4.3) displayed highest photoactivity. By contrast, the rhombohedral samples ( 4‐6 ) showed increased photoactivity with increase in the number of Bi atoms; sample with highest ratio (1.0:6.3) displayed highest photoactivity. Abstract : The rates of decomposition of methylene blue under visible light irradiation in the presence of the calcium bismuthates correlate with the total light absorption by all six bismuthate samples. The photoactivity of the orthorhombic samples increased with a decrease in the number of bismuth species (i. e., [Ca]:[Bi] ratio decreased from 1.0:6.1 to 1.0:4.3), while the photoactivity of the rhombohedral samples increased with increase in the number of bismuth species (i. e., [Ca]:[Bi] ratio increased from 1.0:4.3 to 1.0:6.1).